Trifluoromethyl-imino-bisacetanilide ammonium salts



TRIFLUOROMETHYL-lMlNO-BISACETANILIDE AMMONIUM SALTS Henry Martin, Schafihausen, Switzerland, assignor to Variapat A. G., Basel, Switzerland No Drawing. Application April 14, 1951, Serial No. 221,120

Claims priority, application Switzerland April 21, 1950 3 Claims. (Cl. 260-558) It has been found that new quaternary ammonium compounds containing the trifiuoromethylgroup and showing valuable properties are obtained by reacting halogenated fatty acid amides of the type having an easily exchangeable halogen and where R represents an unsubstituted or substituted alkyl-, aralkyl-, arylor heterocyclic radical and R represents hydrogen, or an alkyl, aralkyl or aryl-group with ammonia or primary, secondary or tertiary aliphatic, aliphatic-araliphatic, aliphatic-hydroaromatic, aliphatic-aromatic, araliphatic, hydroaromatic, aromatic or cyclic amines and treating the so obtained primary, secondary and tertiary amino fatty acid amides with alkylatingor aralkylating agents to obtain the corresponding quaternary compounds. It is a requirement of this invention that in all the above mentioned reactions at least one component containing the trifluoromethylgroup must be used.

The halogen fatty acid amides which are used as starting material are, for instance, prepared by reacting halogen fatty acids or suitable derivatives thereof such as the esters, or halides or anhydrides with primary or secondary amines of the type wherein R is represented by an unsubstituted or substituted alkyl-, aralkyl, aryl or heterocyclic radical and R means hydrogen or an alkyl aralkylor aryl radical.

By way of example there may be cited: dodecylamine, laurylamine mixture C8-Cl2, laurylaniline, a-phenyldodecylamine, p-chlorobenzyl-u-dodecylamine, 4-methylbenzyl-a-dodecylamine, stearylamine, benzylamine, 3,4- dichlorobenzylamine, aniline, toluidine, xylidine, p-chloroaniline, o-chloroaniline, 3,4-dichloroaniline, anisidine, 2,4 dichloroaniline, 2,5 -dichloroaniline, 3 trifluoromethylaniline, 3-trifluoromethyl-4-chloroaniline, 3-trifluoromethyl-6-chloroaniline, 2,4,6-trichloroaniline, 3,4,5- trichloroaniline, pentachloroaniline, 4-chloro-N-ethylaniline, N-ethyl-o-toluidine, 2,6-dimethylani1ine, 1,3-diamino 4 chlorobenzene, 3,4 dichloro N (4 chlorobenzyl) aniline, 3 trifluoromethyl (4' chlorobenzyl)-aniline, benzoyl-p-phenylenediamine, 4-aminodiphenyl, 4-acetamino-4-aminodiphenyl, 4,4'-diaminodiphenyl, 4,4'-diaminostilbene, 4,4'-diaminodiphenylsulphide, 4,4'-diaminodiphenylurea, 4,4-diar ninodiphenylsulphone, 4,4-diamino-maleic-dianilide, 4-amino-2', 4'-dichloro diphenyl ether, 1 amino 2 methoxy 5- trifiuoromethylbenzene, 1-amino-4-trifiuoro-methyl-benzene, 1-amino-2-trifluoromethyl-benzene, 1-amino-3,5- bis trifluoromethylbenzene, 1 amino 2,5 bis trifluoromethylbenzene, 1-amino-2-chloro-5-trifluoromethylbenzene, 1-amino-2-nitro 4-benzotrifluoride, 4-chloro-2 amino-3-trifluoromethyl-1',1'-diphenylether, 2-amino-3- ited States Patent 2 trifluoromethyl-l,1-diphenylether, 4-aminoor Z-aminotrifiuoromethylsulphobenzene, 4-chloro-2-aminophenylmethyl-sulphone, 5,8dichloro-1-naphthylamine, 3'-chloro- 4-methyl-6-methoxy-aniline, 3,4-dichloro-6-methoxyaniline, 4 nitro aniline, diphenylamine, 4,4 dichloro- Z-amino-l,1'-diphenylether, 4-chloro-4-amino-diphenylsulphone, 4 chloro 4' trifluoromethyl 2' aminol,1' diphenylether, 2 aminobenzothiazol, 4 chloro- 3'-amino-diphenyleneoxide, B-amino-phenothioxine, benzhydrylamine, 4,4-dichlorobenzhydrylamine, 4amino-3- tn'fluoromethyl-benzanilide, 4-aminobenzene-3, 4-dichlorosulfanilide, 4-amino-3, 4-dichlorobenzanilide, dichlorocarbazol etc.

When diamines are caused to react there may be used one or two molecular proportions of halogen fatty acid or its derivative.

As halogen fatty acids and their derivatives one may use for example a-halogenoacetic acid, u-halogenopropionicacid, a-halogeno-palmoilfatty acid, fl-halogenopropionic acid, a-halogeno succinic acid, etc.

The preparation of the halogen fatty acid amides is performed in a manner known per se for instance by reaction of the halogenated fatty acid amides with said amines in the presence or absence of solvents.

The reaction of the halogen fatty acid amides thus obtained with the amines defined above may follow by known methods, in which primary up to quaternary amino-fatty acid amides are produced with the aid of ammonia, or primary, secondary or tertiary amines with the elimination of hydrogen halide.

The secondary and tertiary amines used in this process may be substituted on the nitrogen atom by the same or different substituents. All amines may be substituted by any substituent especially by one or more alkyl groups, halogen, trifluoromethylgroups; said amines may be of simple or complex structure and contain one or more heteroatoms.

As such amines to be used in the reaction we mentioned: Ammonia, methylamine, ethylamine, ethanolamine, propylamine, alkylamine, isopropylamine, butylamine, amylamine, isoamylamine, hexylamine, 2-ethylhexylamine, dodecylamine, a. dodecyl benzylamine, benzylamine, phenylethylamine, 4 chlorobenzylamine, 3,4 dichlorobenzylamine, benzhydrylamine, 4,4 dichlorobenzhydrylamine, dimethylamine, diethylamine, methylethylamine, dipropylamine, methylpropylamine, ethylpropylamine, dibutylamine, diamylamine, dihexylamine, di 2 ethylhexylamine, methylbutylamine, di-allylamine, diethanolamine, diethylaminoethanol, dimethylaminoethanol, dipropanolamine, N-methylbenzylamine, N-methy1-4-ch1orbenzylamine, N-ethyl-4-chlorbenzylamine, methylamino-acetic acid-3,4-dichloroanilide, methylamino-acetic acid-3-trifluoromethylanilide, methylamino-acetic acid-3-trifluormethyl 5 chloroanilide, N methyl dodecylamine, N- methyl-a-dodecylbenzylamine, w-methylamino-4-chlorobenzophenon, piperidine, Z-methylpiperidine, morpholine, tetrahydroquinoline, trirnethylamine, triethylamine, N- dimethyl-benzylamine, N-dimethyl-4-chlorobenzylamine, N dimethyl-3,4 dichlorobenzylamine, N -diethyl-3,4-dichlorobenzylamine, dimethylaminoacetic-acid-3-trifiuoromethylanilide, dimethylaminoacetic acid-3,4-dichlorani lide, dimethylaminoacetic-acid-3-trifluoromethyl-4-chloranilide, diethylaminoacetic-acid-3-trifluoromethylanilide, dimethylaminoacetic acid 4 (4 cholorophenoXy)- anilide, dimethylaminoacetic acid-4-trifluoromethylanilide, 4 chlorophenyl-O-dimethyl-aminoethylurethane, 3-

die'thylarnino-dodecylamine, N-dimethyl-a-dodecylbenzylamine, diineth'ylamino ethylene-3,A-dicliolorbnZaniitIe, dimethylaminopropylene 3,4 dichlorobenzamide, dimethylamino ethylen 3 trifiuoromethylbenzenesulfamide, dimethylamino-ethylene-3-trifluoromethyl-4-chlorobenzenesulfonamide, dimethylaminoethylene-3,4-dichlorobenzenesulfonamide, diethylamino-ethylenel-trifiuoromethylbenzolsulfonamide, dirnethylaminoacetic acidphenylester, methylamino-bis-(acetioacid 3 triiiuoromethyl'anilide), N-dimethyll-chlorphenoxy-ethylamine, N,N'-diethylpiperazine, N,N' di 4-chlorobenzylpiperazine, N,N'-di(3,4-dichlorbenzyl)piperazine, piperidinoacetic-acid-3,4-dichloranilide etc.

If for reaction between the halogen fatty acid amides and the above mentioned amines the amines are so chosen that primary, secondary or tertiary amino fatty acid amides are formed a subsequent alkylation or aralkylation is accomplished until the nitrogen atom is quaternarily substituted. This happens with the usual alkylating agents for instancewith the mineral acid esters of satu rated or unsaturated alcohols, for instance alkyl-, aralkylor alkylen-halides, haloge'n-hydrines, dialkylsulphate's or the like, or by addition of sulphonic acid esters. Further alkylating and aralkylating agents especially, for tertiary bases are halogen fatty acid esters, halogen fatty acid amides, halogen alkylurethanes, w-halogenketones, halogenalkylcarbamides, halogenalkylethers, halogenalkylcarbonicacidesters, halogenalkylacylamides, halogenalkylesters and the like.

For all these reactions it is essential that the so obtained quaternary ammonium compounds contain at least one trifiluoromethyl-group. By suitably selecting the components needed in the synthesis one Will be able to obtain specific ammoniumcompounds containing trifluoromethylgroups and having special properties. So the trifiuoromethylgroup may be contained primarily in the halogen fatty acid amides as for example in chloroaceto 3 trifluoromethylanilide, chloroaceto -3 trifluoromethyl 4 chloroanilide, a: chloropropionyl- 3- trifiuorornethylanilide, chloroaceto- 4- trifiuorornethyl'anilide and the like. But the trifiuoromethylgroup may as well be contained in one of the aralkylatinga'gents as for example in halogen fatty acid-3- trifiuoromethylanilide, 3- trifluoromethyl 4 chlorophenyl O chloro -ethylurethane and the like.

According to a further embodiment of th'e'presenflinvention forpreparing ammonium compounds containing trifiuoromethyl-groups, halogen fatty acid esters having a halogen substituent which is capable of reaction are used instead of halogen fatty acid amides. With such esters as for example chloroacetic acid phenolester s quaternary amino-fatty-acidphenolesters are then formed. Said esters may be subsequently aminated into the claimed quaternary ainino-fatty-acid-arnides containing trifluoromethylgroups by treating them for example in aqueous or aqueous-alcoholic solution or emulsion with amines as for example 3-trifiuoromethylaniline whereby the phenol is exchanged.

The new class of quaternary amino 'fatty-acid-arnides containing trifluoromethylgroups may be used for various purposes. By suitable choice of the components one may obtain for example outstanding auxiliariesfor 'textile use as products for protecting wool, furs, feathers and the like from moths and other wool pests asanth renus and attagenus. Dueto theirm'arke'd efiiciency the 'i'i'ew ammonium compounds containing trifiuoroniethylgroiip's are distinguished over other products which have been already proposed for similar purposes. By a suitable substitution one obtains fungicides andha ctericides for diverse fields of application. They may be used as textilejaids or in the proper pest control, for treating seeds or protecting plants. V p

In the following examples the partsare partsby weight except where otherwise stated.

4 Example I (a) 50 parts of dimethylamino aceto-3-trifluoromethyl-4-chloranilide prepared by a known process from 3-trifluoromethyl-4-chloroaniline and chloroacetylchloride and reacting the chloroaceto-3-trifluoromethyl-4- chloroanilide with dimethylamine, are stirred with a small excess of 4 chlorobenzylchloride in 200 parts acetic ether or benzene during 12 hours at 60 C. A white powder precipitates which is filtered off by suction, washed with ether and dried in a vacuum. The new compound is soluble in water and gives clear solutions. Its formula is as follows:

f(b) if as equivalent amount or an excess Olga-dichloro-beii'zylchloride is used'inste'ad of p-c h'lorobenzylchloride the product corresponds to the following formula:

(a) '25 parts dimethylamino-aceto3-trifluoromethylanilide prepared in a manner known per se from trifluoromethylaniline and chloroacet-yl'chloride and treating the chloroaceto- 3-trifiuoromethylanilide with dimethylamine, are boiled with the calculated amount of chloroacetol-chloroanilide in 200 parts acetic other over night. A white powder precipitates which is filtered off -lay-suction, washed with acetic ether and ether and then dried in a vacuum. The new quaternary compound corresponds'to thefollowing formula:

(b) If chlo'i6ac'to-3j4-dihlordanilide is used as aralkylafin'g a gje ht "a ne quaternar eem ounder the following formula'is obtained:

(a) If chloroaceto 3-trifluoromethylanilide is used as aralkylating agent the new quaternary compound corresponds 'tothe following formula:

. Z31 "an; NH-COCHr-N CH5 f CH OON=H"AC OF;

A s ft;alumnae};geifiueieniefliyi mcmcrannies is usedasgralky atiugiagent anew -qliate'rn'a'ry' compound of the following" formula isobtaine'd:

(o 7 01 on. QNH-C 0-CHr-N-OH:

orn-o camQ-m F,

l Example 3 Equimolecular amounts of dimethylamino-aceto-B- trifluoromethyl 4 chloroanilide and chloroaceto-3-trifluoromethyl-4-chloroanilide are boiled in acetic-ether over night, whereby a product which is difficultly soluble in water is separated. This product is filtered by suction washed with acetic-ether and ether; it corresponds to the following formula:

Cl OH: CIQNH-OO-CHrN-0Hr (5111-0 0-NHQC] v Q I i I v F: Example 4 (a) 15 parts it dimethylamino-propionic-acid-3-trifiuoromethyl-4-chloroanilide are dissolved in acetic-ether together with an excess of 3,4-dichlorobenzyl-chloride and boiled with reflux during 12 hours. A white powder is precipitated which is filtered off, washed with aceticether and ether and then dried. It corresponds to the following formula:

(b) If chloroaceto-3-trifluoromethylanilide is used instead of 3,4-dichlorobenzylchloride one obtains a compound of the following formula:

CHI-C 0-NHQCI (b) By similar reaction between diethylaminoaceto-3- trifiuoromethylanilide and chloro-aceto-3-trifluoromethy1- 4-chloroanilide a product of the following formula is obtained: 4 a

6 Example 6 20 gms. of dimethylamino-aceto-3-trifiuoro-methyl-4- chloroanilide and w-chloro-4-chloroacetophenone are dissolved in acetic-ether and boiled several hours. Thereby a new quaternary compound of the following formula is precipitated:

Equimolecular amounts of dimethylamino-aceto-3-trifluoromethyl-4-chloroani1ide and chloroaceto-3,4-dimethylanilide are dissolved in acetic-ether and heated with reflux during several hours. A new quaternary compound of the formula:

l CHr-C O-NH CH:

separates out.

Example 8 (a) Equimolecular amounts of dimethylamino-aceto- 3-fiuoromethyl-4-chloroanilide and 4-chloro-phenyl-O- chloroethyl-urethane are dissolved in chlorobenzene and heated during 24 hours with reflux. The precipitate is filtered, washed with chlorobenzene and dried, it corresponds to the following formula:

| cl-ONn-oo-om-N-on,

| enronro-co-Nng-ol C F;

The same product is obtained by condensation of 4- chlorophenyl-O-dimethylamino-ethylurethane with chloro-aceto-3-trifiuoromethy1-4-chloroanilide.

(b) By a similar reaction of dimethylamino-aceto-3- trifiuoromethylanilide with 3-trifluoromethy1 4 chlorophenyl-O-chloroethyl-urethane or of 3-trifiuor o-methyl-.

4-chlorophenyl-B-dimethylamino-ethylurethane with chloroaceto-3-trifluoromethylanilide a quaternary compound of the following formula is obtained:

Cl CH:

(0) By a similar reaction of dimethylamino-aceto-S- trifluoromethyl-4-chloroani1ide with 3 -trifluoromethylphenyl O chloroethylmethane or of 3-trifluoromethylphenyl-O-dimethylamino-ethylurethane with chloro-aceto- 3-trifluoromethyl-4-chloro-anilide a quaternary compound of the following formula is obtained:

Cl CH:

(d) By a similar reaction of 3-trifluoromethyl-4-chlorophenyl O dimethylaminoethyl-urethane with chloro- 7 8 aceto-3,4:dich1oroanilide a compound of the following solvent is removed. The product is recrystallised from formula 18 obtained: diluted alcohol and corresponds to the following formula:

H. (21) QNH-w-cHr-N-om (17) C F (hm-c O-NH-QO-Qm f (b) By similar reaction of chloroaceto-3-trifluorometh- (ll-ONH-CO-CEh-N-CH; yl-4-chloroanilide with dimet hylarnino-aceto-3-chloro-4- (E (4 '-'chloroplrenoiry') fanilide or at 'dimethyl-aminO-aceto-B- 1 tri'iiuorome'thyl 4=cliloronanilide with chloroaceto-B-chlo- 0F, ro-4-'.(4'-clilorophenoxy,) anilide a product of the follow ing composition "is obtained:

C? "CH i C1 (22) ClQNH-CO-Cflrlf-GH;

cH,-c0--NH- 0-C o1 C-F; Example 9 (0) By a similar r'eaction between "chloroaceto-3-tri- (a) 20 gms. of dimethylamino-ethylene- 3 -trifluoro- 'H11m'oflfethllrtldimmanflme and fi' l f y l QP methyl-4-chlorophenyl-sulfamide prepared by interaction P y the fOHOWlHg of 3 trifiuor'omethyl 4 chlorobenzenesulfochloride on product is obtained:

C] CH: (23) ei'g omenetr cn. I r

du,-oH,-oo-NH--'s-C -o1 CF: asymmetric dimethylethylenediamine, and the calculated (5) By a similar reaction between chloroaceto-4-tricorresponding amount of chloroaceto-3-trifluoromethfluorome't'hyl-anilide and 'diinethylamino-aceto-4-(4-chloylanilide are dissolved in acetic-ether and boiled during rophenoxy)-auilide a condensation product of the fol- 12 hours with reflux, a white powder thereby separates lowing formula is obtained:

. CFIONHCOCH:NCH3 V z-C0'NH-OCl out. It is filtered and washed with acetic-ether and has (6) By 21 Similar C I BII Efi H 0f Chl0r0aC6t0-3-trithe following formula: fluoromethyl-4-chloroanilide and dimethylamino-aceto-Z- 01 CH (18) t' chloropheuoity ifi-chloronanilide-a:product of the fol- O 1 l'owing formula emima; r

NHCO-GHzN-CH| rd on Nn-soor R 01 n, F o1-- NH-CO-QHr-N-CH:

on. F iJHr-OO-NH-G (b) By asimil'ar reaction of dimethylamino-ethyl'ene- 3-trifiuoromethyl-4-chlorophenylsulfonamide with chloroaceti'cacid-3,4-dichloroanilide the product of condensation of the following formula is produced: 0] f This product may also be prepared by reaction of dio1 mz-oo-onfiN-om methylam'ino-acetofa trifluoromthyl-mehloroanilide with L Cl chloroaceto-i fil -chlo r-ophe'noXy') -5 -chloronanilide. 1 (1) By a similar -'reaction of chloroaceto-Ia-trifluoro- CF methyl-anilide and dimethylamino-aceto-2-(4'-chloro- Exam lg 10 5'5 p'lrenoxy) S ti'ifluOromethylaniIide a product is obtained p which co'rresp'ond's to the following formula: 25 'grns. of dimethylamino-propylene-3,4-dichloro- 01 CH benzamide prepared from 3,4-dichlorobenzoyichloride 1 CF; and asym. dimethylaminopropylarnine are reacted with Q the calculated amount of chloroaceto-S-trifluoromethyl-4- HrCO-NH chloroanilide 'in acetic-ether during several hours with reflux. The powder precipitated is filtered otf, washed 6 with acetic ether and dried; it corresponds to the following formula: -o1

or CH; (20) 86 Example 1 2 ClGNHCO-C1Ir-N--OH| I p ,CQFOHrCHrNECO C1 (:13 1'2 'grris. drufet'hyIanuno acetO-Z-chloro-5-trifiuoro- F; methylamlide and the calculated amount of chloreacetyl- 4-chloroanilide are dissolveilin 100 gms. acetic-ether and Exam [6 I C] heated over night on a water-bath. A white precipitate is p separated by filtration washed with acetic-ether and dried (a) 15 gms. chloroaceto-3-trifiuoromethylanilide and in vacuo.

the calculated amount of dimethylamino-aceto-4-(4'- The dimethylamino-aceto-2-chloro-5-trifiuoromethylchlorophenoXy)-'anilide are dissolved in parts *of anili'de-us'cd as starting material is prepared in a manner acetic-ether aud'h'eate'd 2 1 hours with reflux. Thenuhe T known 'per se from 2'chloro-5-trifluoro-methylaniline and chloroacet'ylchloride, e. g. in acetone as solvent and in the presence of potash-solution. By interacting the chloroaceto-2-chloro-5-trifluorornethyl-anilide in aqueous dimethylamine solution at a temperature of about 50 C. the corresponding dimethylamino-acetic-acid-derivative is obtained.

The quaternary product of condensation has the following formula:

(b) By a corresponding condensation of dimethylamino aceto 2 chloro trifluoromethylanilide with chloroacetyl-3-trifluoromethyl-4-chloroanilide or of dimethylamino aceto 3 trifluoromethyl 4 chloroanilide with chloroacetyl 2 chloro 5 trifluoro methylanilide the product with the following constitution is obtained:

| C1 CH:

Example 13 (a) 50 gms. of dimethylamino-aceto-dodecylamide are dissolved in acetic-ether and reacted for 12 hours on a water-bath with the calculated amount of chloro-aceto- 3-trifluoro-methyl-4-chloroanilide. The aqueous solution of the new product foams strongly. The same product is obtained by reaction of chloroacetyl-dodecylamide with dimethylamino-aceto-3-trifluoromethyl-4-chloroanilide. It corresponds to the following formula:

(b) If diethylamino-aceto-dodecylamide is reacted with chloroacetyl-3-trifluoromethyl-anilide, the product obtained has the following constitution:

oHz-o O-NHQCI The reaction may also be executed in a solvent.

(e) By interaction of fi-diethylamino-propionic-acid- 3-trifiuoromethylanilide with laurylbromide a product with the following constitution is obtained:

(f) 20 gms. 4-methyl-u-dodecylbenzyl-N-dimethylamine and the calculated amount of chloroaceto-3-trifluoromethyl-4-chloroani1ide are heated together for several hours at a temperature of 90-95 C. then a shorter time at 120 C. without addition of a solvent until a sample is soluble in water. The quaternary compound so obtained has the following constitution:

CH-CnHn SHPOMHOC,

(g) 16 gms. p-tertiary-octylphenoxy-ethoxyethyl-dimethylamine and the calculated amount of chloroaceto- B-trifluoromethylanilide are dissolved in acetic-ether and heated 12 hours with reflux. A white powder precipitates, which is filtered and recrystallised from alcohol. It has the following constitution: I

g 01 CH;

(c) If asym. dimethylamino-ethylene-palmoil-fattyacide is reacted with chloroacetic-acid-3-trifluoromethyl- 4-chloroanilide in acetic-ether or benzene the quaternary ammonium salt of the following constitution is obtained:

onHn-o ONHC m-cm-n-on,

hm-oo-nnQcu Instead of the p-tertiary-octylphenoxy-ethoxyethyl-dimethylamine one may use the p-tertiary-octyl-o-cresoxyethoXyethyl-dimethylamine.

(11) When asym. dimethylaminopropylene-dodecyl-sulfonamide is reacted with chloro-aceto-4-trifiuoromethylanilide in acetic-ether a water soluble foaming product is obtained having the following constitution:

Example 14 (a) Equivalent amounts of dimethylamino-aceto-3- trifiuoromethyl-4-chloroanilide and chloroaceto-5,8-dichloro-l-naphthylamide was stirred in chlorobenzene during 24 hours at a temperature of -1 10 C. A white powder separates out and is 'fiItered off, washed with 1 1 chlorobenzene and then with ether and dried. It corresponds to the following formula:

. H, Cl-C NH-COCHr-N-CHa (b) If the chloroaceto-5,8-dichloro-1-naphthylamide is replaced by chloroaceto-2,4,S trichloroaniIine the following quaternary ammonium compound is formed:

(0) With chloroaceto-4-chloroanilide as an aralkylating agent one obtains:

21 gms. 'dimethylamino-acetolA-dich1orobenzhydrylamide, prepared from 4,4'-"dichloro-benzhydrylamine and chloroacetylchloride and reacting the chloroacetyl-4,4- dichlorobenzhydrylamide with dime'th'ylamine, are dissolved in acetic-ether, added with the calculated amount of chloroacetyl-3-trifiuoromethyl-alilide and heated for 12 hours on the water-bath. Thereby the quaternary compound of the following formula is precipitated:

Example 16 (a) 15 gms. chlo'roaceto-El-trifluoromethyl-4-chloroanilide are dissolved :in alcohol and treated with a 40% monomethylamine solution while cooling with ice. The methylamino bis (aceto 3 trifluoromethyl 4 chloroanilide) is thus formed. The alcoholic solution is heated in a closed vessel to complete the reaction and after cooling the excess of -dirnethylamine is removed. The solution is diluted with Water, whereby the product is completely precipitated. After crystallisation from alcohol it forms beautiful crystals.

Equim'olecular amounts of this tertiary amine and di methylsulp'hate are dissolved in acetic-ether and heated on the water-bath. An ammonium-compound of the following composition is obtained:

(b) If chloroacetyl-3 trifluoromethylanilide and methylarnine are used as reactants and otherwise worked under the same conditions, methylamino-bis-(aceto-3-trifiuoromethylanil-ide) is obtained. Equivalent amounts of this amine and 3,4-dichlorobenzylchlorid give the following ammonium compound which is diiiicultly solublein water.

Example 117 (a) 8 gms. dim'e'thylamino-aceto-4-trifluoromethylanilide and an excess of 3,4-dichlorobenzyl-chloride are dissolved in chlorobenzene o'r toluene and stirred overnight at the temperature of the water-bath. The product of'con:

densation precipitates inform of a'v'vhite powder which is filtered by suction, was-tree with the same solvent and dried in a vacuum. lthasth'e following formula:

(0) If chloroacetyl-3-trifluoromethyl-4-chloroanilide is used instead of chloroacetyl-3,4-dichloroanilide the fo1- lowing quaternary compound is obtained:

(Ill/CH: o Fro-M1 004? Hr-"N-UH:

chemo-singer Example 18 (a) 0.1 mol 3-trifiuoromethyl-4-chloroaniline is dissolved in acetone and the calculated amount of chloroacetylchloride is added drop by drop. At the same time an aqueous solution of potassium carbonate is also added drop by drop in order to neutralise the hydrochloric acid. The reaction is first performed at room temperature and then on the water-bath. When the reaction has reached its end the reaction mixture is treated with an excess of water whereupon the chloroaceto-3-trifluoromethyl-4- chloroanilide precipitates. This raw product may generally be used for the reaction with amines. The reaction may also be accomplished in benzene, chlorobenzene-and the like.

23 parts chloroaceto-S-trifiuoromemyl-4ch1oroanilide.

are stirred into 60 parts of an aqueous 20% dimethylamine-solution at room temperature and after one hour the whole slowly heated to 50 C. with reflux. The reaction has reached its end when a sample of the inhomogeneous mixture is clearly soluble in diluted hydrochloric acid. After cooling the reaction mixture which forms a semi-solid and an aqueous layer is separated and the non- 2,752,393 l3 l4 aqueous layer washed with water. It generally solidifies The following products of condensation may be prespontaneously or after inoculation. pared in a similar manner as indicated in the foregoing 24 parts dimethylamino-aceto 3 trifluoro-rnethyl-4- examples. (49 chloroanilide and an equivalent amount chloroacetophenylester are dissolved in 200 parts acetic-ether and 5 01 stirred overnight on the water-bath. A white powder C -N O :NG:Hi

precipitates, which after cooling of the reaction mixture 43F Q NH C C1 01- NH-CO-CHrl IC2Hr F JlHr-CHr-O-CO-NH-Q-Cl I is filtered by suction, washed with acetic-ether and dried C1 in a vacuum. It corresponds to the following formula:

C1 NHCOOH2I \I 5 2o Fa bHr-C O-NHOCI (b) If chloroaceto-3-methyl 4 chlorophenyl-ester is (53) C /C2Hs c1 NH-C o-o Hz-N-CzH F orn-oHr-NH-c O--NH QCI used instead of chloroacetophenylester, the following com- I (54) pound is obtained.

(47) NH oo-on E12 01 CH: Q oiOnn-omonr-r r ont F. (LHr-C-NH 01 (F dm-oo-oQox OH The invention is, however, not confined to the cited Example 1 examples and may be extended to any other examples.

According to all processes described the halides of the quaternary compounds are generally obtained. Other salts may be prepared according to known methods for example by double decomposition with other salts.

The quaternary ammonium salt prepared according to Example 18a, is dissolved or suspended in water and an excess of 3,4-dimethylaniline is added thereto. The mixture is then boiled for several hours. More preferably the reaction is accomplished under pressure and it is then not Example 21 necessary to hold the reactants in solution. When the reaction has reached its end the product is treated with steam in order to blow off the xylidine and phenol in excess. The remaining product has the same properties and constitution as that of Example 7.

Instead of 3,4-dimethylaniline other primary or see- Articles from wool are treated in an aqueous bath at 40-60 C. with 0.5% (based on the wool) of the quaternary ammonium compound containing trifluoromethylgroups described in Example 3. Treatment begins in a lukewarm bath whereupon the temperature is slowly raised at 4060 C. where it is held for one hour. Then ondary flmmes il be used 9 example m'chlol'oamlme the wool is rinsed. A so treated article is moth proof 3,4-dlchloroamlme and the llkeand also proof against furand carpet-bugs.

Example I claim is:

1. As new product the quaternary ammonium deriva- 19 chloroacetoa'trifiummethyl4"h1manilide tive of aminoacetic acid amide of the following formula are dissolved in acetic-ether and the equivalent amount of N-3,4-dichlorophenyl N' asym.-dimethylaminoethylurea O added thereto. The mixture is held overnight at waterbath temperature, the product which is precipitated is fil- O NH c1 tered, washed with acetic-ether and then with ether and N -01 dried in a vacuum. It corresponds to the following 0235/ \CHPOO NH G1 formula:

Cl OH:

15 15 being a white powder, clearly soluble in water and pos- 3. A quaternary ammonium compound having the sessing valuable properties for mothproofing textiles and formula:

materials liable to damage from moths and other textile pests, the portion of the molecule Within the brackets bearing a positive change due to unsatisfied pentavalent 5 i E 7 nitrogen and the chlorine outer of the brackets bearing OTNHOGI a negative charge. 1 5

2. The quaternary ammonium salt compound having CF! F: the formula:

3 n S 01 00 CH 2 CO NH 01 References Cited in the file of this patent 1 r UNITED STATES PATENTS were OWBYB y 2,093,115 Wolfram et al. Sept. 14, 1931 where S is a member selected from the group consisting 1 of CE; and C1.

2,343,071 Martin et a1. Feb. 29, 1944 

2. THE QUATERNARY AMMONIUM SALT COMPOUND HAVING THE FORMULA: 